TWI449715B - Co-polymerization of an isoolefin with a halogenated co-monomer - Google Patents

Description

Copolymerization method of isoolefin and halogenated comonomer Field of invention

This invention relates to direct copolymerization of isoolefins with halogenated comonomers. More specifically, the present invention relates to the formation of a brominated copolymer via direct copolymerization of an isoolefin monomer with a 4-bromo-3-methyl-1-butene monomer.

background

Poly(isobutylene-co-isoprene), or IIR, a synthetic elastomer known to us, such as butyl rubber, which has been in the 1940s via isobutylene and a small amount of isoprene (1- 2 mole %) was prepared by random cationic copolymerization. As a result of its molecular structure, the IIR has superior air impermeability, high loss modulus, oxidation stability, and expanded fatigue strength.

The first major use of IIR is in tire inner tubes. Despite the low level of main chain unsaturation (about 0.8-1.8 mol%), for endogenous use, IIR has sufficient cross-linking activity. As the inner liner of tires develops, the curing reactivity of IIR is enhanced to the conventional diene-based elastomers such as butadiene rubber (BR) or styrene-butadiene rubber ( The level found in SBR)) becomes necessary. For this purpose, halogenated grade butyl rubber was developed.

The halobutyl rubber is prepared by halogenation after butyl rubber dissolved in an organic solution. For example, a solution in which IIR is dissolved in hexane is treated with elemental chlorine or bromine to form a chlorobutyl rubber (CIIR) or a bromobutyl rubber (BIIR). These halobutyl rubbers are characterized by the presence of active allylic halides along the polymer backbone. The improved reactivity of these groups (compared to conventional elastomeric unsaturation) increases the cure reactivity of CIIR and BIIR to a level comparable to that of materials such as BR and SBR. This allows for acceptable levels of adhesion between, for example, BIIR-based inner tube formulations and BR-based tire residue mixtures. Not surprisingly, the increased polarization of Br results in a much more active BIIR than CIIR compared to Cl. Thus, BIIR is the most important grade of halobutyl rubber in the business.

This conventional method of manufacturing a halobutyl rubber has various problems. It is first necessary to make butyl rubber, usually at a temperature of -70 to -100 ° C, then separate it from the polymerization diluent (usually methyl chloride), dry it, and then dissolve it in a hexane solution for the elemental chlorine. Or bromine is treated at a temperature of 40 to 65 °C. There are significant energy and solvent costs associated with this multi-stage process. In addition, the halogenation process comprises an aqueous quenching stage which produces a significant volume of acid which requires neutralization prior to disposal. The conventional methods are expensive and comprise a plurality of stages; in order to simplify the process, it is desirable to directly produce a halogenated butyl rubber by copolymerizing an isoolefin with a halogenated comonomer in a single stage process during the polymerization.

Previous attempts have been made to copolymerize isoolefins with halogenated comonomers. In particular, p-bromostyrene (ZA Sadykhov, FMAliev, Azerb. Khim. Zh. 1970, 3, 96) and 2-bromo-2-methyl-1,3-butadiene (European Patent 0 609 737) were used. Try to copolymerize with the brominated comonomer. These attempts have met with limited commercial success. However, there is no report in the literature on the copolymerization of isobutylene (IB) with 4-bromo-3-methyl-1-butene (BMB), and the maintenance of such particular comonomers has therefore not been explored.

Thus, the need for copolymers of isoolefins with halogenated comonomers (specifically brominated comonomers) and simplified processes for making such copolymers remains.

Summary of the invention

The invention comprises an isoolefin copolymerized with a halogenated co-monomer. Preferably, the present invention comprises a halogenated co-monomer which, when copolymerized with an isoolefin monomer, produces a non-vinyl, non-allylic first-stage bromine having a third carbon adjacent thereto. When the halogen is removed, the first stage carbonyl cation is preferably rearranged to a third stage carbonyl cation which subsequently enters a nucleophilic substitution or can undergo elimination, thereby generating a double bond. In this way, a copolymer of an isoolefin and a halogenated co-monomer can be produced with high conversion and selectivity to produce a useful halogenated copolymer in a single stage process.

According to the present invention, there is provided a polymer comprising: a repeating unit derived from at least one isoolefin monomer; and a repeating unit derived from a halogenated co-monomer of the formula: Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine.

The halogenated co-monomer may comprise, for example, 4-bromo-3-methyl-1-butene.

According to another aspect of the present invention, there is provided a cured article made from the above polymer.

According to still another aspect of the present invention, there is provided a process comprising the steps of: preparing a mixture of an isoolefin monomer dissolved in a polymerization diluent and a halogenated comonomer of the formula:

Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine; a cationic generator initiator is added to the mixture in a semi-continuous manner; and, the monomers are reacted to form a polymer.

According to still another aspect of the present invention, there is provided a process comprising the steps of: preparing a solution of a cationic generator initiator in a catalyst solvent; and dissolving the isoolefin in a polymerization diluent in a semi-continuous manner A mixture of a monomer and a halogenated comonomer of the following formula is added to the solution:

Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine; and, reacting the monomers to form a polymer.

Additional features of the invention are set forth in the detailed description which follows.

The invention has been described in detail, and preferred embodiments thereof will now be described with reference to the accompanying drawings.

Detailed description of preferred embodiments

The copolymer is not limited to a particular isoolefin. However, isoolefins in the range of 4 to 16 carbon atoms (specifically 4 to 7 carbon atoms), such as isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, 2-Methyl-2-butene, 4-methyl-1-pentene, and mixtures thereof are preferred. The best is isobutylene.

The halogenated co-monomer may comprise any suitable monomer which, when copolymerized with an isoolefin monomer, produces a non-vinyl, non-allylic first stage bromine having a contiguous third stage carbon. Preferably, the comonomer comprises a linear C ₄ primary bond having an olefin group at one end and a halogen group at the opposite end thereof. More preferably, located comonomer comprising C ₄ alkyl group on the main carbon chain of the third. More preferably, the halogenated co-single system belongs to the following formula:

Wherein R ₂ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine.

More preferably, R ₁ is a C ₁ -C ₄ alkyl group and an R ₂ -based hydrogen or a C ₁ -C ₄ alkyl group. More preferably, R ₁ is a methyl or ethyl group and an R ₂ -based hydrogen. Most preferably, the co-monolithic system 4-bromo-3-methyl-1-butene is halogenated.

The molar ratio of the isoolefin monomer to the halogenated co-monomer can be from 10 to 100. The halogenated co-monomer may be supplied in a weight percentage ratio of 0.02 to 0.3 to the isoolefin, preferably 0.03 to 0.30, more preferably 0.05 to 0.20, still more preferably 0.10 to 0.20.

The copolymer may comprise at least 0.15 mole percent of a halogenated unit derived from a halogenated comonomer, such as a bromination unit. Preferably, the copolymer comprises at least 0.4 mole percent (more preferably at least 1.0 mole percent, even more preferably at least 1.5 mole percent, more preferably at least 2.0 mole percent, and even more preferably at least 2.5 moles %, more preferably at least 3.0 mole %, still more preferably at least 4.0 mole %, optimally 2 to 5 mole % of the halogenated unit derived halogenated unit.

Molecular weight M _n (number average molecular weight) of the copolymer is preferably from 90 to 500 kg based / mole, preferably 150 to 500 kg / mole, more preferably 200-400 kg / mole.

The copolymer is made by dissolving the comonomer in a suitable polymerization diluent. The polymerization diluent may comprise methyl chloride, chloroform or hexane, or any other solvent or mixture of solvents known to those skilled in the art. Preferably, the polymerization diluent comprises methyl chloride.

The cationic generator initiator according to the present invention may comprise a Friedel-Crafts catalyst having the ability to initiate cationic polymerization with an activator, as is known in the art. The cation generator initiator is preferably soluble in the polymerization diluent and may be supplied separately or dissolved in the catalyst solvent. In this case, the catalyst solvent and the polymerization diluent are preferably miscible with each other. The catalyst solvent may comprise methyl chloride, chloroform or hexane. In a preferred embodiment, the catalyst solvent is the same as the polymerization diluent. A preferred example of a suitable cationic generator initiator dissolved in a catalyst solvent is a solution of aluminum chloride (AlCl ₃ ) in methyl chloride. The cation generator initiator can be activated via a suitable proton source, such as water or hydrochloric acid (HCl).

In a continuous process, the catalyst solution can be added to the comonomer at periodic intervals in a semi-continuous manner. Examples of the semi-continuous catalyst addition method include drop addition. Those skilled in the art will appreciate that the term "droplet" does not necessarily mean the relative volume used, and may not be sufficient to cause a reaction after amplification of a "drop" of the catalyst solution. The term is therefore intended to include a semi-continuous addition, preferably a fixed volume of catalyst at periodic intervals.

A continuous process may employ "reverse addition" in which a solution of the comonomer reactant is added to the catalyst solution supplied within the reactor volume under suitable reaction conditions. The reactants can be added to the catalyst solution in a semi-continuous or dropwise manner.

Preferably, the yield of the copolymer is at least 12%, more preferably at least 20%, even more preferably at least 40%, more preferably at least 50%, even more preferably at least 60%, more preferably more preferably At least 70% by mole, still more preferably at least 80%.

In order to increase the halogen content of the copolymer, a subsequent conventional halogenation operation can be carried out. Halogens used in such post-halogenation operations may include bromine or chlorine. In this way, a suitable halogen content can be obtained in the copolymer.

A non-vinyl, non-allylic first-stage bromine having a third-order carbon as a contig is supplied via a 1,2-insertion of BMB in the copolymerization with isobutylene (IB) (see Figure 7). After removal of the bromo group, a first stage carbonyl cation is formed which is known to rearrange to a third stage carbonyl cation. This carbonyl cation may participate in a nucleophilic substitution reaction or may undergo elimination to form a double bond, as shown in Figure 7.

These conditions result in crosslinking or solidification of the copolymer under suitable conditions. Curing can occur via the first stage bromine (ZnO cure) or via a double bond (sulfur cure). The copolymer may comprise a component of a zinc oxide (ZnO) curing system or a sulfur curing system. Curable copolymers can be used in the formation of shaped articles for a variety of applications, particularly in applications where halobutyl rubber is normally used, such as in tire innerliner formulations.

The invention is further illustrated by reference to the following examples.

experiment material

Synthesis of 4-bromo-3-methyl-1-butene Under a nitrogen atmosphere, 285 mg (1.50 mmol) of CuI was added to 285 ml of diethyl ether and stirred at room temperature for 30 minutes. 32 g (149.6 mmol) of 1,4-dibromo-2-butene was added to this solution. After stirring for another 30 minutes at room temperature, the reaction mixture was cooled to -10 ° C and 100 mL (300 mmol) of MeMgI (3.0 M in diethyl ether) was passed through the dropping funnel over 2 hours. Join. The reaction mixture was then allowed to warm to room temperature and stirred for an additional 20 hours. At the end of this period, ice was used to react with excess MeMgI, and the product was extracted several times with diethyl ether. The combined organic extracts were dried over MgSO ₄ : 10.2 g (45%) of 4-bromo-3-methyl-1-butene, boiling point: 110-114 ° C (bp: 110-112) ℃ ^{5 [5]).} Nuclear magnetic resonance (NMR) data is consistent with data supplied in the literature (RW Hoffmann et al, Liebigs Ann. Chem. 1992, 11 , 1137). All chemicals used are purchased from Aldrich.

other materials

Isoprene (IP; from Aldrich) was freshly distilled prior to use. Isobutylene (IB) and methyl chloride (MeCl) from Matheson are dried by flowing through a column packed with BaO and CaCl ₂ and condensed at the reaction temperature. The AlCl ₃ system from Aldrich is used as received.

program

Polymerization All polymerizations were carried out at -80 °C under dry nitrogen in an MBraun Lab Master 130 glove box equipped with an integral cold bath. The cold bath (hexane) was cooled with an FTS Flexi Cool immersion cooler. A 500 ml round bottom flask equipped with a top stirrer was loaded with MeCl, IB, IP or BMB. The polymerization started with the addition of an AlCl ₃ catalyst solution prepared in advance (0.45 g of AlCl ₃ in 50 g of MeCl was premixed at -30 ° C for 30 minutes and then cooled to the reaction temperature). After 5-10 minutes, the polymerization was terminated via the addition of 30 ml of pre-cooled methanol. The obtained polymer was purified by redissolving in hexane, precipitating from methanol and drying in a vacuum oven at +40 °C. The final transformation was determined gravimetrically. The butyl polymerization of the control was carried out before the copolymerization with the brominated monomer. The original formulation used for butyl polymerization was varied by reducing the amount of IB from 60 grams per 200 grams total to 20 grams to avoid formation of a multimodal distribution in the resulting polymer. The formulation used was as follows: IB = 20 g, IP = 0.53 g, MeCl = 179.5 g, AlCl ₃ - catalyst solution = 2 ml.

Polymer and comonomer analysis The molecular weight and molecular weight distribution of the polymer was equipped with six Styragel HR columns (pore size = 100, 500, 10 ³ , 10 ⁴ , 10 ⁵ and 10 ⁶ angstroms) and maintained at 35 °C constant temperature Waters system, DAWN DSP 18-angle laser light scattering detector (Wyatt Technology), Waters 410 DRI detector maintained at 40 °C constant temperature, and Waters 996 photodiode array set at 254 nm The size of the PDA detector was determined by Rejection Chromatography (SEC). Tetrahydrofuran (THF), freshly distilled CaH _{2 was} used as the mobile phase and the system was supplied at a rate of 1 ml/min. The ASTRA software kit (Wyatt Technology) was used to obtain absolute molecular weight data with dn/dc = 0.093. The same value is used for the copolymer due to the combination of less than 2 mole % of the second monomer (IP or BMB). Using CDCl ₃ as a solvent, the ¹ H-NMR spectrum was taken (VMB) at Varian 300 MHz and (polymer) at Bruker 500 MHz NMR.

Results and discussion

Compared with the control butyl experiment, the copolymerization of isobutylene (IB) with 4-bromo-3-methyl-1-butene (BMB) is carried out with different concentrations of BMB and three times higher concentration of AlCl ₃ -catalyst solution. (6 ml) (see Table 1). Unlike the control butyl polymer (1), after the catalyst solution was introduced into the reaction mixture, a thread was observed.

The range of the control butyl polymer (1) based on the desired molecular weight of (M _w (weight average molecular weight) = 430 kg / mole, M _n = 195 kg / mole). If the same amount of BMB (in mole basis) instead of IP, with the polymer (1) Comparative copolymer (2) having the higher of the major M _w (600 kg / mole) but the M _n ( 150 kg / Moel) is lower. The highest molecular weight (copolymer (3): M _w = 880 kg / mole, M _n = 500 kg / mole) via the use of half the number of lines obtained BMB. Copolymerization with double the number of BMB only produce the copolymer (2) the same M _w = 600 kg / mole of copolymer (4), but the M _n = 330 kg / mole in double-based copolymer ( 2 ). All IB-BMB copolymers contain certain low molecular weight fractions (see Figure 1). Compared to the comparative butyl polymerization ( 1 ), although three times more catalyst was used. However, the conversion is still in the range of 12.2-20.0% (see Table 1). Interestingly, the increase in the number of BMBs has no major impact on conversion (see Copolymerization ( 2 ) and ( 4 )). Generally, the increased amount of IP results in a dramatic decrease in copolymer conversion. This means that under the conditions of polymerization, physical effects such as mixing and mass transfer play a considerable role.

The binding of the brominated monomer was confirmed by NMR spectroscopy. Figure 2 shows the ¹ H-NMR spectrum of the copolymer ( 4 ). A characteristic signal for the free-state monomer (multiple line at 5.75 ppm) could not be found in the spectrum, indicating the formation of a true copolymer. The broad signal that can be around 3.3 ppm is attributed to the proton of the bromomethylene unit (~CH ₂ Br) derived from the 1,2- or 1,3-bonding of the brominated monomer represented in Figure 8. .

Theoretically, the structure of the allyl group similar to that found in bromobutyl (shown in Figure 9) can be derived from 1,2-binding.

The simulated spectra of these allyl structures (using ACDLabs proton NMR simulation software) supported the absorption of 5.39 ppm and 3.8-3.9 ppm (see Figure 2-4) from the structure of the allyl group. The simulated spectrum also supports signals at 4.65 ppm, 4.85 ppm, and 5.15-5.2 ppm (see Figures 2 and 4) which may be due to the assumption of protons of olefins derived from the structure in Figure 10.

For the calculation of the molar % of the combination of bromomethylene units in the copolymer, the following equation is used: (i) 7x+8y = integral area of aliphatic protons (100 in Figure 2) (ii) 2x = integral area of olefin protons with Br-coordination → x = (olefin protons with Br-coordination) The integral area is /2→substituting x in (i), and solving the equation for y

Moer % (combined comonomer) = [x / (x + y)]. 100%

According to the above calculation, the copolymer ( 4 ) had a combination of 0.41 mol% of bromination units. This copolymer also had a content of the olefin structure shown in Fig. 10 of 0.13 mol% (calculation: 6x + 8y = 100). Table 2 shows the calculated mole % of BMB which is incorporated into the copolymers ( 2 )-( 4 ). The binding of BMB is in the range of 0.15-0.41 mol%.

The inventors also calculated the reactivity ratio for the IB-BMB system according to the following equation: r _IB =ln(1-C _IB )/ln(1-C _ScBr ), where C = conversion in fractions

The r _IB value shows that for IB, BMB is less active than IP.

All of the copolymers described so far contain certain low molecular weight fractions (see Figure 1) and low conversion grades (12.2-20.0%). Furthermore, the % MoM of BMB incorporated in the copolymer is not very high (see Table 2).

In order to improve the yield and the binding of BMB, the method of adding the AlCl ₃ -catalyst solution to the reaction mixture is varied. Three different methods of catalyst addition were used: the catalyst was added semi-continuously (dropwise) over a period of 5.5 minutes; it was continuously sprayed into the reaction vessel using a curved tip needle; and the catalyst was injected into the reaction vessel in a single injection in. The concentration of BMB is also changed. For these copolymerizations, 40 grams of IB (400 grams of total reaction weight) was used to obtain sufficient material for the curing experiment. As can be seen from the conversion data from the copolymerization ( 5 )-( 7 ), the method of catalyst addition has a strong influence on the final yield.

^a) [IB] = 1.8 mol/L; AlCl ₃ catalyst solution: 12 ml; solvent: MeCl; total reaction weight: 400 g; temperature = -80 °C. ^{b) The} B.# system is defined as follows: [(BMB) wt% / (IB wt%)] × 100. (s) the catalyst is sprayed; (d) the catalyst is added dropwise; (i) the catalyst is directly injected into the reaction mixture.

The highest yield (51%, copolymer ( 6 )) was obtained when the catalyst solution was added dropwise. This polymerization is initially initiated with a fine dispersion and ends at the end of the catalyst introduction, such as a large rubber ball. Using a continuous spray process, a yield of 24% (copolymer ( 8 )) was produced. After the introduction of the catalyst solution, the formation of a polymer thread was observed. When the catalyst solution was injected in a single injection, almost the same conversion (20%, copolymer ( 10 )) was obtained. By varying the BMB concentration (copolymers ( 5 )-( 7 ) and ( 9 )), no significant effect on the conversion data was observed.

Use different methods of adding the catalyst together with the same BMB concentration (copolymer (6), (8) and (10)) did effect of molecular weight M _w and M _n. In "the spray" method (copolymer (8)) the lowest of the M _w (900 kg / mole) and M _n (90 kg / mole), and the "drop-adding" method of producing the highest having M _w ( 1,320 kg / mole) and M _n (350 kg / mole) copolymer of (6). Referring to Table 3, the molecular weight data, it can be seen, increasing the BMB concentration causing decrease of M _n. The BMB concentration has no significant effect on _Mw .

The NMR spectra of the copolymers ( 5 )-( 10 ) showed signals for protons of olefins at 4.65 ppm, 4.85 ppm, 5.2 ppm, and 5.4 ppm. These signals may be attributed to the structure shown in FIG. The signal showing a combination of brominated structures (~3.3 ppm for the bromomethylene unit and 3.8 ppm and 4.5 ppm for the allyl group shown in Figure 9) is weak or completely absent. When treated differently (redissolved in hexane and without precipitation in MeOH), the copolymer exhibited signals of these properties, indicating that the brominated structure is most likely present in the low molecular weight portion of the copolymer.

Since the polymerization method used so far cannot increase the BMB content in the copolymer, the order of addition of the reactants is varied in the effort to improve the bonding. The AlCl ₃ catalyst solution was first supplied to the reaction vessel before the dropwise addition (reverse addition) of the monomer mixture (IB/BMB (IP)). Moreover, after introduction of the IB/BMB mixture to the AlCl ₃ catalyst solution, polymer strands were observed. Using this novel procedure, the concentration of the BMB and AlCl ₃ catalyst solutions was varied (see Table 4). For some copolymerizations, the IB number is amplified to 40 grams and sufficient material is available for the curing experiment.

The results obtained for the comparative butyl polymerizations ( 11 ) and ( 12 ) show that the order of addition of the catalyst solution and the monomer mixture affects the molecular weight and conversion. Comparing, by using the inverse adding procedure (copolymer _{(12)), M w,} M n and a decrease in the yield of the copolymer (11). BMB inverse added to the polymerization procedure, to obtain a M _w = 610 kg / mole and M _n = 265 kg / mole of copolymer (13). In comparison with the comparative butyl polymerization ( 12 ), the molecular weight of the copolymer ( 13 ) is very high, and the BMB is a chain transfer agent which is weaker than IP. The yield of the copolymer ( 13 ) was 58%. A comparable control butyl polymer ( 12 ) conversion was 41%. These conversion data are in contrast to the data obtained for the normal polymerization procedure (see copolymers ( 1 ) and ( 2 ) in Table 1).

Using the amplified formulation of copolymerization ( 13 ), the resulting copolymer ( 14 ) has a higher molecular weight and yield. A significant increase in molecular weight and yield due to a 5 fold increase in BMB compared to copolymerization ( 15 ) (see copolymerization ( 16 )). The increase in the amount of BMB also results in a drastic reduction in the conversion of the copolymer. This is in contrast to the results obtained using normal polymerization procedures (see copolymerizations ( 2 ) and ( 4 ) in Table 1). In comparison to the normal polymerization procedure (see Figure 1), the SEC traces of copolymers ( 13 )-( 16 ) showed no low molecular weight fraction.

In addition to yield and molecular weight distribution, novel polymerization procedures also affect the structure of the copolymer obtained. Referring to Fig. 5, since the characteristic signal of the free state BMB (multiple line at 5.75 ppm) disappeared, the ¹ H-NMR spectrum of the copolymer ( 14 ) showed the formation of a true copolymer. However, according to this spectrum, there is no bromine functionality in the copolymer (no signal of protons of bromomethylene units (~CH ₂ Br) in the vicinity of 3.3 ppm). As shown in Figure 6, the signals at 5.4 ppm, 5.2 ppm, 4.85 ppm, and 4.65 ppm can be attributed to the protons of the olefin derived from the structure shown in Scheme 4. The content of the structure of the olefins incorporated in the copolymers ( 13 )-( 16 ) is in the range of 0.05 to 0.07 mol%.

Briefly, the reverse addition of the catalyst solution to the monomer mixture results in a higher yield and the formation of a compressible low molecular weight fraction as compared to the normal polymerization procedure. The copolymer obtained by the reverse addition procedure did not show any bromine functionality.

Curing Using ZnO and/or sulfur formulations, curing experiments were performed on certain copolymers. For all of the copolymers tested, curing did occur, producing a rubbery (albeit weak) sheet. A small difference (0.5-0.8 dNm) in the torque range was observed using the sulfur solidification method (related to the C=C double bond). The ZnO cure also showed only a slight cure due to the low level of bromine end groups in the copolymer tested.

The above description of the preferred embodiments of the invention, as well as further features and embodiments of the invention, will be apparent to those skilled in the art. The following patent claims are to be interpreted broadly by reference to the foregoing, and the inventors, etc.

1 shows a copolymer (1) - (4) of the SEC trace; FIG. 2 shows a copolymer (4) of the spectrum of 500MHz ¹ H-NMR; FIG. 3 shows a copolymer provided in FIG. 2 (4) of the 500 MHz ¹ An enlarged view of the aliphatic region of the H-NMR spectrum; Figure 4 shows an enlarged view of the olefin region of the 500 MHz ¹ H-NMR spectrum of the copolymer ( 4 ) provided in Figure 2; Figure 5 shows the 500 MHz of the copolymer ( 14 ) ¹ H-NMR spectrum; Figure 6 shows an enlarged view of the olefin region of the 500 MHz ¹ H-NMR spectrum of the copolymer ( 14 ) provided in Figure 5; Figure 7 shows the possible elimination reaction of the brominated copolymer with sulfur curing Or possible subsequent crosslinking with ZnO curing; Figure 8 shows the different combinations of brominated monomers; Figure 9 shows the structure of the allyl derived from the 1,2-binding of BMB; and Figure 10 shows the olefin The structure of the signal.

Claims (20)

A polymer comprising the following: a) a repeating unit derived from at least one isoolefin monomer; and b) a repeating unit derived from a halogenated co-monomer of the formula: Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine. The polymer of claim 1 wherein the R ₁ is a C ₁ to C ₄ alkyl group and wherein the R ₂ is hydrogen. The polymer of claim 1 wherein the halogenated co-monosystem is 4-bromo-3-methyl-1-butene. The polymer of any one of claims 1 to 3, wherein the X-based bromine and the polymer thereof comprise at least 0.15 mol% of a bromination unit. The polymer of any one of claims 1 to 3, wherein the X-ray bromine and the polymer thereof comprise from 2 to 5 mol% of a bromination unit. The polymer according to any one of 1 to 3, as requested item, having 150 to 500 kg / mole with a molecular weight (M _n). A cured article made from a polymer of any one of claims 1 to 6. The solidified article of claim 7, wherein the article is used from the polymer Manufactured by a zinc oxide curing system. A method of preparing a polymer comprising the following: a) supplying a mixture of an isoolefin monomer dissolved in a polymerization diluent and a halogenated comon monomer of the following formula: Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine, b) adding a cationic generator initiator to the mixture in a semi-continuous manner; and c) reacting the monomers to form the polymer. The method of claim 9, wherein the catalyst solvent and/or the polymerization diluent is methyl chloride, chloroform or hexane. The method of claim 9 or 10, wherein the addition of the semi-continuous addition of the cation generator initiator is in the form of a drop. The method of claim 9 or 10, wherein the isoolefin monomer has a molar ratio of 10 to 100 for the halogenated comonomer. The method of claim 9 or 10, wherein the polymer is produced by 1,2-insertion of the halogenated co-monomer in the isoolefin. The method of claim 9 or 10, wherein the transformation is at least 20%. A method of preparing a polymer comprising the following: a) supplying a solution of a cationic generator initiator in a catalyst solvent; b) halogenating the isoolefin monomer dissolved in the polymerization diluent in a semi-continuous manner with the following formula A mixture of co-monomers is added to the solution: Wherein R ₁ is a C ₁ -C ₂₀ alkyl group, a C ₁ -C ₂₀ linear or branched olefin group, or a substituted aromatic hydrocarbon, R ₂ is hydrogen or a C ₁ -C ₂₀ alkyl group, and X is a bromine group. Or chlorine, and c) reacting the monomers to form the polymer. The method of claim 15, wherein the catalyst solvent and/or the polymerization diluent is methyl chloride, chloroform or hexane. The method of claim 15 or 16, wherein the semi-continuous addition of the monomer mixture to the cation generator initiator is in the form of a drop. The method of claim 15 or 16, wherein the isoolefin monomer has a molar ratio of 10 to 100 for the halogenated comonomer. The method of claim 15 or 16, wherein the polymer is produced by 1,2-insertion of the halogenated co-monomer in the isoolefin. The method of claim 15 or 16, wherein the transformation is at least 50%.